WO2022075471A1 - Électrolyte solide à base de sulfure de type vitrocéramique et procédé de fabrication associé - Google Patents

Électrolyte solide à base de sulfure de type vitrocéramique et procédé de fabrication associé Download PDF

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WO2022075471A1
WO2022075471A1 PCT/JP2021/037459 JP2021037459W WO2022075471A1 WO 2022075471 A1 WO2022075471 A1 WO 2022075471A1 JP 2021037459 W JP2021037459 W JP 2021037459W WO 2022075471 A1 WO2022075471 A1 WO 2022075471A1
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solid electrolyte
sulfide solid
glass ceramics
sulfide
electrolyte glass
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PCT/JP2021/037459
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English (en)
Japanese (ja)
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恒太 寺井
徳仁 近藤
剛士 牧野
淳 佐藤
弘幸 樋口
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出光興産株式会社
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Priority to EP21877770.4A priority Critical patent/EP4227276A1/fr
Priority to CN202180068224.4A priority patent/CN116348427A/zh
Priority to KR1020237011466A priority patent/KR20230079084A/ko
Priority to US18/030,286 priority patent/US20230378525A1/en
Priority to JP2022555604A priority patent/JPWO2022075471A1/ja
Publication of WO2022075471A1 publication Critical patent/WO2022075471A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C10/00—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/32—Non-oxide glass compositions, e.g. binary or ternary halides, sulfides or nitrides of germanium, selenium or tellurium
    • C03C3/321—Chalcogenide glasses, e.g. containing S, Se, Te
    • C03C3/323—Chalcogenide glasses, e.g. containing S, Se, Te containing halogen, e.g. chalcohalide glasses
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C10/00—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition
    • C03C10/16—Halogen containing crystalline phase
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C4/00—Compositions for glass with special properties
    • C03C4/14—Compositions for glass with special properties for electro-conductive glass
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C4/00—Compositions for glass with special properties
    • C03C4/18—Compositions for glass with special properties for ion-sensitive glass
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
    • H01B1/10—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances sulfides
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0561—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of inorganic materials only
    • H01M10/0562—Solid materials
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0065—Solid electrolytes
    • H01M2300/0068—Solid electrolytes inorganic
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present invention relates to sulfide solid electrolyte glass ceramics and a method for producing the same.
  • a sulfide solid electrolyte As a solid electrolyte used for the solid electrolyte layer, a sulfide solid electrolyte has been conventionally known, and improvement of ionic conductivity is desired for this sulfide solid electrolyte.
  • the ionic conductivity is determined by the type and composition ratio of the raw material used, the heat treatment temperature, and the like.
  • the sulfide solid electrolyte has been improved in ionic conductivity by optimizing its crystal type (Patent Document 1). Further, by paying attention to the crystallite diameter of the solid electrolyte and increasing it to improve the ionic conductivity (Patent Document 2), or by using a complexing agent having a tertiary amino group in the production of the solid electrolyte. It has also been attempted to reduce the content of crystalline Li 3 PS 4 in the obtained solid electrolyte (Patent Document 3).
  • the present invention has been made in view of such circumstances, and provides sulfide solid electrolyte glass ceramics having high ionic conductivity, improved water resistance, and improved initial irreversible capacity when used as a battery.
  • the sulfide solid electrolyte glass ceramics according to the present invention are In X-ray diffraction (XRD) measurement using CuK ⁇ ray, it has peaks at 20.2 ° and 23.6 °, the crystallite diameter is 30 nm or more, and P 2 S obtained from solid 31 P-NMR measurement. 6 4- Phosphorus ratio is 4.5 mol% or less, which is a sulfide solid electrolyte glass ceramics.
  • the method for producing the sulfide solid electrolyte glass ceramics according to the present invention is as follows.
  • the present invention provides sulfide solid electrolyte glass ceramics having high ionic conductivity, improved water resistance, and improved initial irreversible capacity when used as a battery, and also the sulfide solid electrolyte glass ceramics. Can be provided with a method of manufacturing.
  • FIG. 1 It is a flow figure explaining an example of the form of the manufacturing method of this embodiment. It is a figure (X-ray diffraction (XRD) measurement) explaining the calculation method of a crystallography. It is a figure (X-ray diffraction (XRD) measurement) explaining the calculation method of a crystallography. It is an exposure test device for water resistance evaluation. It is the X-ray diffraction (XRD) measurement result of the solid electrolyte (A1) obtained in the step (A) of Example 1. FIG. It is the X-ray diffraction (XRD) measurement result of the solid electrolyte (B1) obtained in the step (B) of Example 1. FIG.
  • XRD X-ray diffraction
  • the present embodiment an embodiment of the present invention (hereinafter, may be referred to as “the present embodiment”) will be described.
  • the numerical values of the upper limit and the lower limit relating to the numerical range of "greater than or equal to”, “less than or equal to”, and “to” are numerical values that can be arbitrarily combined, and the numerical values of the examples are used as the numerical values of the upper limit and the lower limit. You can also do it.
  • the present inventors have found the following matters and have completed the present invention.
  • the sulfide solid electrolyte has PS 43- as a main skeleton .
  • a sulfide solid electrolyte whose peak has been confirmed to be observed at a specific position by XRD measurement has been obtained, further improvement is required in the ionic conductivity and water resistance of the sulfide solid electrolyte obtained thereby. there were.
  • Patent Document 1 does not prepare a battery using the obtained sulfide solid electrolyte and evaluate the battery characteristics such as the initial irreversible capacity thereof.
  • Patent Document 2 attempts to increase the crystallite diameter, it is around 20 nm as shown in Table 1, and there is still room for improvement. Furthermore, no attention was paid to the P2 S 6 4 - phosphorus ratio, and the battery characteristics such as the initial irreversible capacity were not confirmed.
  • Patent Document 3 does not pay attention to the crystallite diameter and the P2 S 6 4 - phosphorus ratio, and does not confirm the battery characteristics such as the initial irreversible capacity.
  • the present inventors have diligently studied the sulfide solid electrolyte of Patent Document 1, and the solid electrolytes of Patent Document 2 and Patent Document 3.
  • the position of the peak obtained by X-ray diffraction (XRD) measurement of the sulfide solid electrolyte glass ceramics, the crystallite diameter described later, and the P2 S 6 4- phosphorus ratio obtained from the solid 31 P - NMR measurement should be below a specific value. I focused on doing. Ions of sulfide solid electrolyte glass ceramics by having a peak at a specific position, setting the crystallite diameter to a specific value or more, and setting the P2 S 6 4 - phosphorus ratio to a specific value or less.
  • Irreversible capacity at the time of initial cycle which is one of the battery characteristics required from CV measurement when the battery is made into a battery with improved conductivity and water resistance
  • the irreversible capacity is the irreversible capacity unless otherwise specified. It was found that the irreversible capacity (meaning the initial irreversible capacity) at the time of the initial cycle can be suppressed. At the same time, it has been found that the sulfide solid electrolyte glass ceramics can be obtained in high yield by the above-mentioned production method.
  • the sulfide solid electrolyte glass ceramics has a peak at a specific position in X-ray diffraction (XRD) measurement, has a specific crystallite diameter, and has a P2 S 6 4- phosphorus ratio obtained from solid 31 P - NMR measurement. Is less than or equal to a certain value, and these characteristics are events that have never been recognized so far. Further, in the method for producing the sulfide solid electrolyte glass ceramics, the ionic conductivity and water resistance of the sulfide solid electrolyte glass ceramics are improved only by changing the method of adding the raw materials conventionally used, and the ionic conductivity and the water resistance can be obtained from the improvement.
  • the battery has an excellent irreversible capacity, and this embodiment is an extremely excellent manufacturing method.
  • a method for producing a modified sulfide solid electrolyte powder according to the first to thirteenth aspects of the present embodiment will be described.
  • the sulfide solid electrolyte glass ceramics according to the first aspect of the present embodiment is In X-ray diffraction (XRD) measurement using CuK ⁇ ray, it has peaks at 20.2 ° and 23.6 °, the crystallite diameter is 30 nm or more, and P 2 S obtained from solid 31 P-NMR measurement. 6 4- Phosphorus ratio is 4.5 mol% or less, which is a sulfide solid electrolyte glass ceramics.
  • the determination of the P2S 6 4- phosphorus ratio obtained from the X-ray diffraction (XRD) measurement using CuK ⁇ ray and the solid 31 P - NMR measurement can be carried out by, for example, the method described in Examples.
  • the sulfide solid electrolyte of the invention described in Patent Document 1 has a peak at a specific position by X-ray diffraction (XRD) measurement, but the crystallite diameter of the sulfide solid electrolyte is completely different. I'm not paying attention. Furthermore, no attention is paid to the P2 S 6 4- phosphorus ratio obtained from the solid 31 P - NMR measurement. Therefore, it cannot be said that the ionic conductivity and water resistance are sufficiently high. Further, in Patent Document 1, the battery characteristics such as the irreversible capacity of the battery manufactured from the obtained sulfide solid electrolyte have not been studied.
  • Patent Document 2 describes the crystallite diameter of the solid electrolyte, it is not sufficiently large and pays no attention to the P2S 6 4- phosphorus ratio obtained from the solid 31 P - NMR measurement. not. Therefore, it cannot be said that the ionic conductivity and water resistance are sufficiently high. Further, in Patent Document 2, the battery characteristics such as the irreversible capacity of the battery manufactured from the obtained sulfide solid electrolyte have not been studied.
  • Patent Document 3 does not pay attention to the crystallite diameter of the solid electrolyte and the P2 S 6 4- phosphorus ratio obtained from the solid 31 P - NMR measurement. Therefore, there is room for improvement in ionic conductivity and water resistance. Further, in Patent Document 2, the battery characteristics such as the irreversible capacity of the battery manufactured from the obtained sulfide solid electrolyte have not been studied.
  • the crystallite diameter is set to a specific value or more, and P 2S 6 4- phosphorus obtained from solid 31 P - NMR measurement.
  • the sulfide solid electrolyte glass ceramics can improve the ionic conductivity and water resistance, and can further suppress the irreversible capacity when made into a battery.
  • the reason why the sulfide solid electrolyte glass ceramics according to the first aspect has excellent ionic conductivity and water resistance is not clear, but an increase in crystallite diameter means a decrease in the ratio of grain boundaries. do. Since it is considered that lithium ion diffusion is suppressed at the grain boundaries and moisture easily penetrates, the reduction of the grain boundaries improves the ionic conductivity and water resistance. It is hypothesized that the effect becomes remarkable above a specific crystallite diameter. According to the studies by the inventors, it is known that the P2 S 6 4 - component is easily hydrolyzed.
  • the P2 S64 component itself acts as a factor that inhibits the ionic conduction of Li ions and also inhibits the crystal growth of the solid electrolyte, and if this component is large, the crystallite diameter may not be sufficiently large. There is. Therefore, when the phosphorus ratio of P2 S 64 of the sulfide solid electrolyte glass ceramics is 4.5 mol% or less, the water resistance and the ionic conductivity are improved. In addition, the P 2 S 6 4- component traps Li ions in the solid electrolyte and may accelerate the deterioration of the battery, and the phosphorus of the P 2 S 6 4- component of the sulfide solid electrolyte glass ceramics. By setting the ratio to 4.5 mol% or less, it can be expected that the oxidation characteristics of the battery will be improved.
  • the irreversible capacity is suppressed and the reason why the battery characteristics are excellent is not clear, but the chemical stability of the solid electrolyte due to the reduction of the crystal grain boundaries is not clear.
  • the effect of improving the ionic conductivity and the effect of improving the oxidation characteristics by setting the P2 S 6 4 - phosphorus ratio to a specific value or less, the lithium ion consumed during the initial charge and discharge of the battery The hypothesis is that this is because the amount decreases.
  • the P 2 S 6 4- phosphorus ratio can be determined by solid 31 P-NMR, and can be carried out, for example, by the method described in Examples.
  • the sulfide solid electrolyte glass ceramics according to the second aspect of this embodiment is It is a sulfide solid electrolyte glass ceramic having only one exothermic peak having an intensity of 0.15 W / g or more at 310 ° C. or lower in a differential thermal analysis (DTA).
  • the differential thermal analysis (DTA) measurement can be performed, for example, by the method described in Examples.
  • the sulfide solid electrolyte glass ceramics of the present invention usually have one crystallization exothermic peak below 310 ° C., which is caused by the transition from a high conduction crystal to a low conduction crystal, and suppresses this transition. It is preferable to keep it. In rare cases, it may have two crystallization exothermic peaks below 310 ° C.
  • the peak on the low temperature side is related to the precipitation of high conduction crystals, and the fact that this remains means that the growth of high conduction crystals is insufficient, and it is preferable to eliminate it. In summary, in the temperature range of 310 ° C.
  • ionic conductivity is improved by controlling so that only one crystallization peak having an intensity of 0.15 W / g or more is provided at 310 ° C. or lower. Therefore, it is preferable.
  • the sulfide solid electrolyte glass ceramics according to the third aspect of this embodiment is The ratio of the mole fraction of Li 2S (I Li 2S) to the mole fraction of P 2 S 5 (I P2S 5 ) calculated from the element ratio measured by an inductively coupled plasma (ICP) emission spectroscopic analyzer (I Li 2S / IP2S5 ) is sulfide solid electrolyte glass ceramics having a value of 2.6 or more and 3.3 or less. Measurement by an inductively coupled plasma (ICP) emission spectrophotometer can be performed, for example, by the method described in Examples.
  • ICP inductively coupled plasma
  • the ratio of the mole fraction of Li 2S (I Li 2S) to the mole fraction of P 2 S 5 (I P2S 5 ) (I Li 2S / I P2S 5 ) is within a specific range.
  • the P2 S 6 4 - component which is an impurity of the solid electrolyte, can be reduced, and the ionic conductivity and water resistance are improved.
  • the remaining amount of Li 2S is small, which leads to the reduction of free sulfur atoms, the improvement of water resistance, and the suppression of the irreversible capacity when used as a battery.
  • the sulfide solid electrolyte glass ceramics according to the fourth aspect of this embodiment is Solid sulfide solid electrolyte A sulfide solid having a phosphorus ratio of P2 S 6 4- obtained from solid 31 P - NMR measurement of the solid electrolyte (B), which is an intermediate for producing glass ceramics, of 15.0 mol% or less. Electrolyte glass ceramics.
  • the solid electrolyte (B) is obtained in the step (B) of the eighth aspect described later, and is a production intermediate for producing the sulfide solid electrolyte glass ceramics.
  • the P 2 S 6 4- component in the solid electrolyte (B) itself inhibits the ionic conduction of Li ions and also acts as a factor in inhibiting the crystal growth of the solid electrolyte (B).
  • the child diameter may not be large enough.
  • the P2S64 component is easily hydrolyzed as described above.
  • the phosphorus ratio of P2 S 6 4- of the solid electrolyte (B) is 15.0 mol% or less because the ionic conductivity and water resistance are improved.
  • the sulfide solid electrolyte glass ceramics according to the fifth aspect of the present embodiment is In the differential thermal analysis (DTA) of the solid electrolyte (B), which is an intermediate for the production of sulfide solid electrolyte glass ceramics, the half-price range of the exothermic peak that first appears at a temperature of 130 ° C or higher during the heating process is 8.0 ° C.
  • DTA differential thermal analysis
  • the half price width of the exothermic peak that first appears at a temperature of 130 ° C. or higher in the temperature raising process is set to 8.0 ° C. or lower.
  • the sulfide solid electrolyte glass ceramics according to the sixth aspect of the present embodiment is A sulfide solid electrolyte glass ceramic containing a lithium atom, a phosphorus atom, a sulfur atom and a halogen atom.
  • a lithium atom it is preferable to include a lithium atom, a phosphorus atom, a sulfur atom and a halogen atom because the ionic conductivity and water resistance are further improved.
  • the sulfide solid electrolyte glass ceramics according to the seventh aspect of the present embodiment is
  • the halogen atom is at least one selected from a chlorine atom, a bromine atom and an iodine atom, which is a sulfide solid electrolyte glass ceramics.
  • the halogen atom is at least one selected from chlorine atom, bromine atom and iodine atom because ionic conductivity and water resistance are further improved.
  • the method for producing the sulfide solid electrolyte glass ceramics according to the eighth aspect of the present embodiment is The step (A) of treating Li 2 S and P 2 S 5 with at least one selected from stirring, mixing and pulverization to obtain a solid electrolyte (A), and the solid electrolyte (A), Li 2 S and lithium halide
  • the sulfide solid electrolyte glass ceramics according to the first to seventh aspects described above can be obtained with high efficiency. That is, the sulfide solid electrolyte glass ceramics having improved ionic conductivity and water resistance can be produced according to the eighth aspect.
  • the sulfide solid electrolyte glass ceramics has PS 43- as a main skeleton. However, it also contains subskeletons such as P 2 S 6 4- and P 2 S 7 4- , and in order to improve the ionic conductivity of the sulfide solid electrolyte glass ceramics, the P 2 S 6 4- phosphorus ratio should be used. It is effective to reduce it.
  • P2S 74- is known to have extremely poor water resistance, and it is preferable to reduce this component as well.
  • the solid electrolyte (A) is obtained in the step (A), and then the solid electrolyte (B) is obtained in the step (B).
  • sulfide solids with sub - skeletons such as P2 S 6 4- and P 2 S 7 4- lead to deterioration of the characteristics of sulfide solid electrolyte glass ceramics when synthesized in two stages in this way. It became clear that the content in the electrolyte glass ceramics could be controlled, and the production method according to the eighth aspect was reached.
  • the sulfide solid electrolyte glass ceramics contains not only the main skeleton PS 4 3- but also sub-skeletons such as P 2 S 6 4- and P 2 S 7 4- , but the solid electrolyte (A) ) Is the same. However, it is preferable that the subskeleton of the solid electrolyte (A) exists as P2 S 74- . This is because, in step (B), P 2 S 7 4- reacts with Li 2 S and is easily converted into PS 43 , which is the main skeleton.
  • the solid electrolyte (A) contains Li 4 P 2 S 7 and the solid electrolyte. A method for producing a sulfide solid electrolyte glass ceramics in which the P2 S 7 4- phosphorus ratio measured by 31 P - NMR in (A) is 20.0 mol% or more has been reached.
  • the solid electrolyte (A) further contains P2 S 7 4-, and the phosphorus ratio of P 2 S 7 4- in the solid electrolyte (A) is 20.0 mol% or more. Therefore, the Li 2S added in the step (B) can be sufficiently consumed and the water resistance is improved, which is preferable (Li 2 S is one of the factors for lowering the water resistance). Further, although some P2S 74 - derived from the solid electrolyte (A) remains in the solid electrolyte (B), it does not matter because it almost disappears when it is subsequently heated to form glass ceramics.
  • P 2 S 6 4- does not decrease even when heated.
  • the P 2 S 7 4- phosphorus ratio and the P 2 S 6 4- phosphorus ratio in the solid electrolyte (A) tend to contradict each other.
  • the former is 20.0 mol% or more
  • the P 2 S 6 4- phosphorus ratio in the solid electrolyte (A) becomes sufficiently small
  • the P 2 S 6 4 -phosphorus ratio in the solid electrolyte (B) also becomes small. Therefore, as described in the fourth aspect, the ionic conductivity and water resistance are improved, and the battery is preferable because the irreversible capacity is suppressed.
  • the method for producing the sulfide solid electrolyte glass ceramics according to the tenth aspect of the present embodiment is as follows.
  • the solid electrolyte (B) is a method for producing a sulfide solid electrolyte glass ceramic having PS 43- as a main skeleton.
  • the solid electrolyte (B) has PS 43- as the main skeleton because the ionic conductivity and water resistance are improved.
  • the method for producing the sulfide solid electrolyte glass ceramics according to the eleventh aspect of the present embodiment is as follows.
  • the solid electrolyte (B) is an amorphous sulfide solid electrolyte
  • the method for producing the sulfide solid electrolyte glass ceramics according to the twelfth aspect of the present embodiment is as follows.
  • This is a method for producing solid electrolyte glass ceramics.
  • the amorphous solid electrolyte (B) is heated to a glass ceramic at a temperature in the above region to obtain ionic conductivity and ionic conductivity. It is preferable because the water resistance is greatly improved.
  • the method for producing the sulfide solid electrolyte glass ceramics according to the thirteenth aspect of the present embodiment is A method for producing a sulfide solid electrolyte glass ceramic, which comprises further heating the solid electrolyte (A).
  • the amorphous solid electrolyte (A) it is preferable to heat the amorphous solid electrolyte (A) to form a glass ceramic because the ionic conductivity and water resistance of the sulfide solid electrolyte glass ceramics of the present invention are significantly improved.
  • the amorphous solid electrolyte (A) containing P 2 S 7 4- is obtained and then heated or the like, the P 2 S 7 4- phosphorus ratio is further improved, and the P 2 S 6 4- phosphorus ratio is accordingly increased. Is reduced. It is preferable because the low P2S 6 4 - phosphorus ratio can be maintained or reduced even through the subsequent step (B) and the ionic conductivity is further improved.
  • the battery using the sulfide solid electrolyte glass ceramics according to the fourteenth aspect of the present embodiment is It is a battery using the sulfide solid electrolyte glass ceramics according to any one of 1 to 7 of this embodiment.
  • the ionic conductivity and water resistance are significantly improved, and the irreversible capacity is suppressed.
  • the sulfide solid electrolyte glass ceramics of the present embodiment are preferably obtained by heating an amorphous sulfide solid electrolyte, which will be described later, and are measured by X-ray diffraction (XRD) using CuK ⁇ rays. It is required to have peaks at .2 ° and 23.6 ° and a crystallite diameter of 30 nm or more. The peak position and crystallite diameter by X-ray diffraction (XRD) measurement using CuK ⁇ rays can be determined, for example, by the method described in Examples.
  • the crystal structure of the sulfide solid electrolyte glass ceramics of the present embodiment is preferably a thiolithicon region type II crystal structure in that higher ionic conductivity can be obtained.
  • the "thio-lithicon region II type crystal structure” is a Li 4-x Ge 1-x P x S4 system thio-lithicon region II (thio-LISION Region II) type crystal structure, Li 4 -x Ge 1-x . It is shown that it has one of the crystal structures similar to the PxS4 system thio- LISION Region II type. Further, the sulfide solid electrolyte glass ceramics of the present embodiment may have the above-mentioned thiolycycon region type II crystal structure or may have as the main crystal, but may have higher ionic conductivity. From the viewpoint of obtaining, it is preferable to have it as a main crystal.
  • the sulfide solid electrolyte glass ceramics of the present embodiment preferably do not contain crystalline Li 3 PS 4 ( ⁇ -Li 3 PS 4 ) from the viewpoint of obtaining higher ionic conductivity.
  • Li 7 P 3 S 11 crystal structure 15.3 °, 25.2 °, 29.6 °, 31.0 °
  • Li 4-x Ge 1-x P x S4 system thioli Li 4-x Ge 1-x P x S4 system thioli .
  • the sulfide solid electrolyte glass ceramics of the present embodiment preferably do not contain crystalline Li 3 PS 4 ( ⁇ -Li 3 PS 4 ).
  • 9 and 13 show an example of X-ray diffraction measurement of the sulfide solid electrolyte glass ceramics of the present embodiment.
  • composition formulas Li 7-x P 1- y S y S 6 and Li 7 + x P 1-y S y S 6 having the structural skeleton of the above-mentioned Li 7 PS 6 and having a part of P substituted with Si (Li 7-x P 1-y S y S 6 ).
  • the crystal structure represented by the composition formula Li 7-x-2y PS 6-xy Cl x (0.8 ⁇ x ⁇ 1.7, 0 ⁇ y ⁇ -0.25 x + 0.5) is preferably cubic.
  • 2 ⁇ 15.5 °, 18.0 °, 25.0 °, 30.0 °, 31.4 °, 45.3 °, 47. It has peaks appearing at 0 ° and 52.0 °.
  • the crystal structure represented by the composition formula Li 7-x PS 6-x Ha x (Ha is Cl or Br, x is preferably 0.2 to 1.8) is preferably a cubic crystal and is a CuK ⁇ ray.
  • the crystallite diameter of the sulfide solid electrolyte glass ceramics of the present embodiment is required to be 30 nm or more. From the viewpoint of improving ionic conductivity and water resistance, it is preferably 33 nm or more, more preferably 35 nm or more, further preferably 40 nm or more, further preferably 70 nm or more, and even more preferably 80 nm.
  • the above is more excellent and preferable, and as will be described later, by crystallization after the step (A), the crystallite diameter of the sulfide solid electrolyte glass ceramics can be further increased. In such a case, the crystallite diameter can be further increased. It is even more preferable that it is 90 nm or more.
  • the upper limit is not particularly limited, but is preferably 300 nm or less, more preferably 250 nm or less, and more preferably 200 nm or less from the viewpoint of ease of manufacturing, procurement, and manufacturing of batteries and the like. Is more preferable, 150 nm or less is further preferable, and 130 nm or less is more excellent and preferable.
  • the sulfide solid electrolyte glass ceramics of the present embodiment requires that the P2S 6 4- phosphorus ratio determined from the solid 31 P - NMR measurement be 4.5 mol% or less. In order to improve ionic conductivity and water resistance and suppress irreversible capacity, it is preferably 4.0 mol% or less, more preferably 3.0 mol% or less, and 2.5 mol% or less. It is more preferably 2.2 mol% or less, and more preferably 2.0 mol% or less. The smaller the P2 S 6 4 - phosphorus ratio is, the more preferable it is, and the lower limit is not particularly limited, and it may be substantially 0 mol% or more. Substantially means that 0 mol% also includes below the detection limit.
  • the smaller the P2 S7 4- phosphorus ratio is preferably from the viewpoint of the ionic conductivity of the sulfide solid electrolyte, preferably 20.0% or less. It is more preferably 9.0% or less, further preferably 8.0% or less, and the lower limit is preferably close to 0%.
  • the sulfide solid electrolyte glass ceramics of the present embodiment preferably has only one exothermic peak having an intensity of 0.15 W / g or more at 310 ° C. or lower because the ionic conductivity is improved. It is more preferably 0.20 W / g or more, and further preferably 0.25 W / g or more.
  • the upper limit is preferably 5.0 W / g or less, more preferably 3.0 W / g or less, further preferably 1.0 W / g or less, and 0.80 W / g or less. Is even more preferable.
  • the exothermic peak of the sulfide solid electrolyte glass ceramics of the present embodiment is preferably 200 ° C. or higher and 350 ° C. or lower, more preferably 230 ° C. or higher and 320 ° C. or lower, and 250 ° C. or higher and 300 ° C. or lower. More preferred.
  • the sulfide solid electrolyte glass ceramics of the present embodiment have a mole fraction of Li 2S ( I Li 2S ) and a mole fraction of P 2 S 5 calculated from the element ratio measured by an inductively coupled plasma (ICP) emission spectroscopic analyzer.
  • ICP inductively coupled plasma
  • the ratio (I Li2S / I P2S5 ) of the fraction fraction (I P2S5 ) is 2.60 or more and 3.30 or less
  • the irreversible capacity when used as a battery is increased in order to improve ionic conductivity and water resistance. It is preferable to suppress it, and it is more preferably 2.70 or more and 3.20 or less, and further preferably 2.90 or more and 3.10 or less from the viewpoint of improving ionic conductivity and water resistance.
  • the measurement by the ICP emission spectrophotometer can be measured by, for example, the method described in Examples.
  • the sulfide solid electrolyte glass ceramics of the present embodiment preferably contain a lithium atom, a phosphorus atom, a sulfur atom and a halogen atom.
  • the "sulfide solid electrolyte” is an electrolyte that maintains a solid at 25 ° C. under a nitrogen atmosphere, and contains lithium atoms, sulfur atoms, and phosphorus atoms, and has ionic conductivity due to the lithium atoms. It is a solid electrolyte. It is preferable to further contain a halogen atom if necessary.
  • the halogen atom is at least one selected from a chlorine atom, a bromine atom and an iodine atom.
  • a bromine atom or an iodine atom When only one type of halogen atom is contained, it is preferably a bromine atom or an iodine atom, and more preferably an iodine atom.
  • the combination of chlorine atom and bromine atom, the combination of chlorine atom and bromine atom, or the combination of bromine atom and iodine atom is preferable, and the combination of bromine atom and iodine atom is more preferable. ..
  • the ionic conductivity and water resistance can be further improved, and the irreversible capacity of the battery can be suppressed.
  • the term "main skeleton" means that the phosphorus ratio of PS 43-unit (PS 4 3 - phosphorus ratio) exceeds 50.0%, and the high ionic conduction of the sulfide solid electrolyte.
  • the PS 43 - phosphorus ratio is preferably 60.0 % or more, more preferably 70.0% or more, further preferably 80.0% or more, and the upper limit. The value is not particularly limited and should be close to 100%.
  • the ratio of PS 4 3- unit (PS 4 3- phosphorus ratio), the proportion of P 2 S 7 4- unit (P 2 S 7 4- phosphorus ratio) and P 2 S 6 4- unit.
  • the ratio (P 2 S 6 4- phosphorus ratio) is obtained by measuring the 31 P MAS NMR spectrum (solid 31 P NMR spectrum) and separating the waveforms, respectively, PS 43- unit and P 2 S 7 4- . It means the ratio of the peak area of the unit and P2 S 6 4 - unit to the whole.
  • the detailed conditions for measuring the solid 31 P NMR spectrum are not particularly limited, but the measurement may be performed based on, for example, various conditions described in Examples.
  • the "sulfide solid electrolyte” includes both a crystalline sulfide solid electrolyte having a crystal structure and an amorphous sulfide solid electrolyte.
  • the crystalline sulfide solid electrolyte is a sulfide solid electrolyte in which a peak derived from the sulfide solid electrolyte is observed in the X-ray diffraction pattern in the X-ray diffraction measurement, and the sulfide solid in these. It is a material regardless of the presence or absence of a peak derived from the raw material of the electrolyte.
  • the crystalline sulfide solid electrolyte contains a crystal structure derived from the sulfide solid electrolyte, and even if a part of the crystal structure is derived from the sulfide solid electrolyte, all of the crystal structure becomes the sulfide solid electrolyte. It may be a derived crystal structure.
  • the crystalline sulfide solid electrolyte may contain an amorphous sulfide solid electrolyte as long as it has the above-mentioned X-ray diffraction pattern, and is amorphous. It does not have to contain the sulfide solid electrolyte.
  • the crystalline sulfide solid electrolyte includes so-called glass ceramics obtained by heating the amorphous sulfide solid electrolyte to a crystallization temperature or higher.
  • the sulfide solid electrolyte glass ceramics of the present embodiment is a crystalline sulfide solid electrolyte containing an amorphous component.
  • a peak of the crystal structure derived from the sulfide solid electrolyte and a halo pattern derived from the amorphous sulfide solid electrolyte are observed in the X-ray diffraction pattern in the X-ray diffraction measurement. It is a sulfide solid electrolyte.
  • the amorphous sulfide solid electrolyte is a halo pattern in which the X-ray diffraction pattern is substantially not observed in the X-ray diffraction measurement, and is derived from the raw material of the sulfide solid electrolyte. It means that the presence or absence of the peak of the above, or the presence or absence of a small amount of crystals inevitably generated by the operation when isolating the amorphous sulfide solid electrolyte is irrelevant.
  • the shape of the sulfide solid electrolyte glass ceramics of the present embodiment is not particularly limited, and examples thereof include particles.
  • the average particle size ( D50 ) of the sulfide solid electrolyte glass ceramics of the present embodiment in the form of particles can be exemplified in the range of 0.01 ⁇ m to 500 ⁇ m and 0.1 to 200 ⁇ m, for example.
  • the average particle size (D 50 ) can be measured by, for example, a laser diffraction / scattering type particle size distribution measuring device (for example, LA-950V2 model LA-950W2 manufactured by HORIBA).
  • the ionic conductivity of the sulfide solid electrolyte glass ceramics of the present embodiment obtained by the production method of the present embodiment is extremely high due to the high PS 43- phosphorus ratio, and is usually 0.01 mS / cm or more. Can be. It is preferably 4.50 mS / cm or more, preferably 4.80 mS / cm or more, and preferably 5.00 mS / cm or more.
  • the method for producing the sulfide solid electrolyte glass ceramics of the present embodiment is as shown in FIG.
  • the production method of the present embodiment is preferable because the above-mentioned sulfide solid electrolyte glass ceramics capable of improving ionic conductivity and water resistance and suppressing irreversible capacity when used as a battery can be obtained.
  • the step (A) of the present embodiment requires that Li 2 S and P 2 S 5 are treated with at least one selected from stirring, mixing and pulverization described later to obtain a solid electrolyte (A).
  • the solid electrolyte (A), Li 2S and lithium halide obtained in the step (A) are treated with at least one selected from stirring, mixing and pulverization described later, and the solid electrolyte is treated. It is necessary to obtain (B).
  • the solid electrolyte (A) may be taken out after the completion of the step (A), and Li 2S and lithium halide may be added to the obtained solid electrolyte (A) for treatment, or the step (A) may be performed.
  • the treatment of the step (A) and the step (B) of the present embodiment needs to be at least one selected from stirring, mixing and pulverization.
  • Stirring, mixing and pulverization may be performed alone or in combination, but pulverization is preferable from the viewpoint of setting the particle size of the sulfide solid electrolyte in the range described later.
  • the processes of the steps (A) and (B) may be the same or different, but they are preferably the same, and from the viewpoint of not complicating the manufacturing process, they are continuously used using the same processing apparatus. It is more preferable to carry out the process.
  • the processing of this embodiment can be performed using a mixer, a stirrer, a crusher, or the like. This is because the raw materials can be mixed even if a stirrer is used, and the raw materials are crushed in the crusher, but the mixing also occurs at the same time.
  • Examples of the stirrer and the mixer include a mechanical stirring type mixer capable of stirring (mixing by stirring or stirring and mixing) by providing a stirring blade in the reaction vessel.
  • Examples of the mechanical stirring type mixer include a high-speed stirring type mixer and a double-arm type mixer.
  • Examples of the high-speed stirring type mixer include a vertical axis rotary type mixer and a horizontal axis rotary type mixer, and either type of mixer may be used.
  • the shapes of the stirring blades used in the mechanical stirring type mixer include blade type, arm type, anchor type, paddle type, full zone type, ribbon type, multi-stage blade type, double arm type, excavator type, and biaxial blade type.
  • Examples thereof include a flat blade type and a C type blade type, and from the viewpoint of accelerating the reaction of raw materials more efficiently, a shovel type, a flat blade type, a C type blade type, an anchor type, a paddle type, a full zone type and the like are preferable.
  • Anchor type, paddle type and full zone type are more preferable.
  • the rotation speed of the stirring blade may be appropriately adjusted according to the capacity of the fluid in the reaction vessel, the temperature, the shape of the stirring blade, etc., and is not particularly limited, but is usually 5 rpm or more and 400 rpm or less. From the viewpoint of accelerating the reaction of the raw material more efficiently, it is preferably 10 rpm or more and 300 rpm or less, more preferably 15 rpm or more and 250 rpm or less, and further preferably 20 rpm or more and 200 rpm or less.
  • the temperature conditions for mixing using a mixer are not particularly limited, and are, for example, usually ⁇ 30 to 120 ° C., preferably ⁇ 10 to 100 ° C., more preferably 0 to 80 ° C., still more preferably 10 to 60 ° C. Is.
  • the mixing time is usually 0.1 to 500 hours, preferably 1 to 450 hours, more preferably 10 to 425 hours, still more preferably 20 to 400, from the viewpoint of making the dispersed state of the raw materials more uniform and promoting the reaction. The time, more preferably 30 to 375 hours.
  • the method of performing mixing accompanied by pulverization using a pulverizer is a method conventionally adopted as a mechanical milling method.
  • the crusher for example, a medium-type crusher using a crushing medium can be used.
  • the medium-type crusher is roughly classified into a container-driven crusher and a medium-stirring crusher.
  • Examples of the container-driven crusher include a stirring tank, a crushing tank, a ball mill combining these, a bead mill, and the like.
  • the medium stirring type crusher includes an impact type crusher such as a cutter mill, a hammer mill, and a pin mill; a tower type crusher such as a tower mill; a stirring tank type crusher such as an attritor, an aquamizer, and a sand grinder; Distribution tank type crushers such as pearl mills; distribution tube type crushers; general type crushers such as coball mills; continuous dynamic type crushers; various crushers such as single-screw or multi-screw kneaders.
  • a ball mill or a bead mill exemplified as a container-driven crusher is preferable in consideration of ease of adjusting the particle size of the obtained sulfide.
  • crushers can be appropriately selected according to a desired scale and the like, and if the scale is relatively small, a container-driven crusher such as a ball mill or a bead mill can be used, and a large-scale or mass-produced crusher can be used. In the case of chemical conversion, another type of crusher may be used.
  • a wet pulverizer capable of dealing with wet pulverization is preferable.
  • the wet crusher include a wet bead mill, a wet ball mill, a wet vibration mill, etc., and the conditions of the crushing operation can be freely adjusted, and the beads can be easily crushed with a smaller particle size.
  • a dry medium crusher such as a dry bead mill, a dry ball mill, a dry planetary ball mill, and a dry vibration mill
  • a dry crusher such as a dry non-medium crusher such as a jet mill
  • a circulation type crusher capable of circulating operation to circulate as needed can also be used. Specific examples thereof include a crusher that circulates between a crusher (crushing mixer) that crushes the slurry and a temperature holding tank (reaction vessel).
  • the size of the beads and balls used in the ball mill and the bead mill may be appropriately selected according to a desired particle size, processing amount, etc.
  • the diameter of the beads is usually 0.05 mm ⁇ or more, preferably 0.1 mm ⁇ or more. It is more preferably 0.3 mm ⁇ or more, and the upper limit is usually 5.0 mm ⁇ or less, preferably 3.0 mm ⁇ or less, and more preferably 2.0 mm ⁇ or less.
  • the diameter of the ball is usually 2.0 mm ⁇ or more, preferably 2.5 mm ⁇ or more, more preferably 3.0 mm ⁇ or more, and the upper limit is usually 30.0 mm ⁇ or less, preferably 20.0 mm ⁇ or less, more preferably 15.0 mm ⁇ or less.
  • the material include metals such as stainless steel, chrome steel and tungsten carbide; ceramics such as zirconia and silicon nitride; and minerals such as agate.
  • the number of rotations varies depending on the scale of processing, so it cannot be said unconditionally, but it is usually 10 rpm or more, preferably 20 rpm or more, more preferably 50 rpm or more, and the upper limit is It is usually 1,000 rpm or less, preferably 900 rpm or less, more preferably 800 rpm or less, still more preferably 700 rpm or less.
  • the crushing time in this case cannot be unconditionally determined because it varies depending on the scale of the treatment, but is usually 5 hours or more, preferably 10 hours or more, more preferably 20 hours or more, still more preferably 30 hours or more.
  • the upper limit is usually 300 hours or less, preferably 200 hours or less, and more preferably 100 hours or less.
  • the rotation speed of the rotor By selecting the size and material of the medium (beads, balls) to be used, the rotation speed of the rotor, the time, etc., mixing, stirring, pulverization, and a combination of these processes can be performed, and the obtained sulfide can be obtained.
  • the particle size and the like can be adjusted.
  • solvent In the above mixing, a solvent can be added to the above raw materials and mixed.
  • various solvents widely referred to as organic solvents and the like can be used.
  • a solvent conventionally used in the production of solid electrolytes can be widely adopted, and for example, hydrocarbons such as an aliphatic hydrocarbon solvent, an alicyclic hydrocarbon solvent, and an aromatic hydrocarbon solvent can be widely adopted. Examples include solvents.
  • Examples of the aliphatic hydrocarbon include hexane, pentane, 2-ethylhexane, heptane, octane, decane, undecane, dodecane, tridecane and the like
  • examples of the alicyclic hydrocarbon include cyclohexane and methylcyclohexane.
  • Examples of the aromatic hydrocarbon solvent include benzene, toluene, xylene, mesitylene, ethylbenzene, tert-butylbenzene, trifluoromethylbenzene, nitrobenzene and the like.
  • a solvent containing a hetero element such as a carbon element and an element other than a hydrogen element, for example, a nitrogen element, an oxygen element, a sulfur element, and a halogen element
  • a solvent for example, an ether solvent, an ester solvent, an alcohol solvent, an aldehyde solvent, and a ketone solvent, which contain an oxygen element as a hetero element, are also preferable.
  • ether solvent examples include dimethyl ether, diethyl ether, tert-butyl methyl ether, dimethoxymethane, dimethoxy ethane, diethylene glycol dimethyl ether (digrim), triethylene oxide glycol dimethyl ether (triglycer), and aliphatic ethers such as diethylene glycol and triethylene glycol; Alicyclic ethers such as ethylene oxide, propylene oxide, tetrahydrofuran, tetrahydropyran, dimethoxytetratetratetratetramethyl ether, dioxane; heterocyclic ethers such as furan, benzofuran and benzopyran; methylphenyl ether (anisole), ethylphenyl ether, dibenzyl Aromatic ethers such as ether and diphenyl ether are preferably mentioned.
  • ester solvent examples include methyl formate, ethyl formate, methyl acetate, ethyl acetate, propyl acetate, isopropyl acetate; methyl propionate, ethyl propionate, dimethyl oxalate, diethyl oxalate, dimethyl malonate, diethyl malonate, and succinic acid.
  • Alicyclic esters such as dimethyl and diethyl succinate; alicyclic esters such as methyl cyclohexanecarboxylate, ethyl cyclohexanecarboxylate, dimethyl cyclohexanedicarboxylic acid; methyl pyridinecarboxylate, methyl pyrimidinecarboxylate, acetlactone, propiolactone, butyrolactone , Valerolactone and the like; aromatic esters such as methyl benzoate, ethyl benzoate, dimethylphthalate, diethylphthalate, butylbenzylphthalate, dicyclohexylphthalate, trimethyltrimethylate and triethyl trimellitate are preferable.
  • alcohol solvents such as ethanol and butanol
  • aldehyde solvents such as formaldehyde, acetaldehyde and dimethylformamide
  • ketone solvents such as acetone and methyl ethyl ketone
  • the solvent containing a nitrogen element as a hetero element include a solvent having a group containing a nitrogen element such as an amino group, an amide group, a nitro group and a nitrile group. These can also be used as a complexing agent for forming a solid electrolyte into a complexing agent.
  • examples of the solvent having an amino group include aliphatic amines such as ethylenediamine, diaminopropane, dimethylethylenediamine, diethylethylenediamine, dimethyldiaminopropane, tetramethyldiaminomethane, tetramethylethylenediamine (TMEDA) and tetramethyldiaminopropane (TMPDA); Alicyclic amines such as cyclopropanediamine, cyclohexanediamine, bisaminomethylcyclohexane; heterocyclic amines such as isophoronediamine, piperazine, dipiperidylpropane, dimethylpiperazin; phenyldiamine, tolylene diamine, naphthalenediamine, methylphenylenediamine, Aromatic amines such as dimethylnaphthalenediamine, dimethylphenylenediamine, tetramethylphenylenediamine, and tetramethylna
  • the solvent containing a halogen element as a hetero element include dichloromethane, chlorobenzene, trifluoromethylbenzene, chlorobenzene, chlorotoluene, bromobenzene and the like.
  • the solvent containing a sulfur element dimethyl sulfoxide, carbon disulfide and the like are preferably mentioned.
  • the amount of the solvent used is preferably 100 mL or more, more preferably 500 mL or more, still more preferably 1 L or more, still more preferably 2 L or more, still more preferably 2 L or more, based on 1 kg of the total amount of the raw materials. It is 4 L or more, and the upper limit is preferably 50 L or less, more preferably 20 L or less, still more preferably 15 L or less, still more preferably 12 L or less. When the amount of the solvent used is within the above range, the raw materials can be efficiently reacted.
  • mixing When mixing is performed using a solvent, it may include drying the fluid (usually slurry) obtained by mixing after mixing.
  • the complexing agent When the complexing agent is used as the solvent, the complexing agent is removed from the complex containing the complexing agent, and when the complexing agent and the solvent are used in combination, the complexing agent is formed from the complex containing the complexing agent.
  • a sulfide can be obtained by removing the agent and removing the solvent, or by removing the solvent when a solvent other than the complexing agent is used.
  • the obtained sulfide has a structure possessed by a solid electrolyte such as PS 43- unit , and exhibits ionic conductivity due to an alkali metal element such as a lithium element and a sodium element.
  • Drying can be performed on the fluid obtained by mixing at a temperature depending on the type of solvent. For example, it can be carried out at a temperature equal to or higher than the boiling point of the complexing agent. Further, it is usually dried under reduced pressure at 5 to 100 ° C., preferably 10 to 85 ° C., more preferably 15 to 70 ° C., still more preferably about room temperature (23 ° C.) (for example, about room temperature ⁇ 5 ° C.) using a vacuum pump or the like. It can be carried out by (vacuum drying) to volatilize the complexing agent and, if necessary, the solvent used.
  • Drying may be performed by filtering the fluid using a glass filter or the like, solid-liquid separation by decantation, or solid-liquid separation using a centrifuge or the like.
  • a solvent other than the complexing agent is used, sulfide is obtained by solid-liquid separation.
  • the complexing agent incorporated into the complex may be removed by performing solid-liquid separation and then drying under the above temperature conditions.
  • the fluid is transferred to a container, and the supernatant is obtained after the sulfide (or the complex (which may also be referred to as a precursor of sulfide) if it contains a complexing agent) is precipitated.
  • the sulfide or the complex (which may also be referred to as a precursor of sulfide) if it contains a complexing agent) is precipitated.
  • Decantation for removing complexing agents and solvents, and filtration using, for example, a glass filter having a pore size of about 10 to 200 ⁇ m, preferably 20 to 150 ⁇ m is easy.
  • the drying may be performed after the mixing and before the hydrogen treatment described later, or after the hydrogen treatment.
  • Li 2 S and P 2 S 5 In the production method of this embodiment, it is necessary to use Li 2 S (lithium sulfide) and P 2 S 5 (diphosphorus pentasulfide).
  • the Li 2S used in this embodiment is preferably particles.
  • the average particle size ( D 50 ) of the Li 2S particles is preferably 10 ⁇ m or more and 2000 ⁇ m or less, more preferably 30 ⁇ m or more and 1500 ⁇ m or less, and further preferably 50 ⁇ m or more and 1000 ⁇ m or less.
  • the average particle size (D 50 ) is the particle size at which the particles with the smallest particle size are sequentially integrated to reach 50% of the total when the particle size distribution integration curve is drawn, and the volume distribution is For example, it is an average particle size that can be measured by using a laser diffraction / scattering type particle size distribution measuring device.
  • P 2 S 5 those having the same average particle size as the Li 2 S particles are preferable, that is, those having the same range as the average particle size of the Li 2 S particles are preferable.
  • Li 2 S is added in step (A) and step (B), and P 2 S 5 is added in step (A).
  • step ( A ) 1.00 mol of Li 2S from the viewpoint of optimizing the content of P2 S 74 in the solid electrolyte (A) and preparing a sulfide solid electrolyte glass ceramic having high ionic conductivity.
  • it is preferable to use 0.34 mol or more of P 2 S 5 more preferably 0.38 mol or more, further preferably 0.40 mol or more, and preferably 0.70 mol or less. It is more preferable to use 0.60 mol or less, and further preferably 0.55 mol or less.
  • the sulfide solid electrolyte glass ceramics have PS 43 as the main skeleton, and P 2 S 64 in the sulfide solid electrolyte.
  • P 2 S 64 in the sulfide solid electrolyte.
  • Li 2S is added at least in step (A) and step (B). From the viewpoint of reducing the P 2 S 6 4- phosphorus ratio in the sulfide solid electrolyte and achieving high ionic conductivity, 1.00 mol of Li 2 S used in step (A) is compared with that of step (B). Li 2S is preferably used in an amount of 0.10 mol or more, more preferably 0.20 mol or more, further preferably 0.25 mol or more, preferably 0.80 mol or less, and 0.70 mol or less. It is more preferable to use less than a molar amount, and even more preferably 0.65 mol or less.
  • Li 2 S and P 2 S 5 commercially available commercially available ones can be used, but those prepared by the method adjusted by the method described in Examples may also be used.
  • the purity of Li 2 S is preferably 95% by mass or more, more preferably 98% by mass or more, and P 2 S 5 is P 4 from the viewpoint of improving the ionic conductivity of the sulfide solid electrolyte glass ceramics. From the viewpoint of improving the ionic conductivity of the sulfide solid electrolyte based on S10, the purity is preferably 95% by mass or more, and more preferably 98% by mass or more.
  • lithium halide in order to introduce a halogen atom into the sulfide solid electrolyte from the viewpoint of obtaining the sulfide solid electrolyte glass ceramics having high ionic conductivity, it is necessary to further add lithium halide in the step (B).
  • the lithium halide at least one selected from lithium chloride, lithium bromide and lithium iodide is more preferable, and a combination of lithium chloride and lithium bromide, or a combination of lithium bromide and lithium iodide is further preferable.
  • the amount of lithium halide used may be any as long as it satisfies the preferable compounding ratio (molar ratio) of the above-mentioned lithium atom, sulfur atom, phosphorus atom and halogen atom.
  • the solid electrolyte (A) is a solid electrolyte obtained in the step ( A), and is preferably a sulfide solid electrolyte having PS 4 3- or P2 S 7 4- as the main skeleton, preferably PS 4 3- . It is more preferable that the sulfide solid electrolyte has the main skeleton.
  • the term "main skeleton" means that the phosphorus ratio (PS 43- phosphorus ratio) of PS 43 - units exceeds 50.0 %, and the high ionic conduction of the sulfide solid electrolyte.
  • the PS 43 - division is preferably 60.0 % or more, more preferably 70.0% or more, further preferably 80.0% or more, and the upper limit.
  • the value is not particularly limited and should be close to 100%, but is preferably 99.5% or less, more preferably 98.0% or less, from the viewpoint of achieving both ease of manufacture and ionic conductivity. It is more preferably 95.0% or less.
  • the solid electrolyte (A) preferably contains P2 S 7 4- . Further, Li 2 S and P 2 S 5 used as raw materials in a small amount, PS 4 3 3 which is the target product, and P 2 S 6 4 4 may be further contained. Of these, when the content of P 2 S 6 4- in the sulfide solid electrolyte increases, it leads to a decrease in ionic conductivity, so it is preferable to reduce the content.
  • step (B) Li 2S and lithium halide are further added to the solid electrolyte (A) containing Li 4 P 2 S 7 to obtain a sulfide solid electrolyte, which is contained in the sulfide solid electrolyte glass ceramics.
  • the P 2 S 6 4- phosphorus ratio can be reduced and the ionic conductivity is improved. Therefore, from the viewpoint of improving the ionic conductivity of the sulfide solid electrolyte glass ceramics, the P2 S7 4 - phosphorus ratio measured by 31 P - NMR in the solid electrolyte (A) is the total amount of the solid electrolyte (A).
  • the standard is 20.0 mol% or more, more preferably 30.0 mol% or more, further preferably 35.0 mol% or more, and the upper limit is not particularly limited, but the step. Since PS 43- is generated when the treatment of (A) is performed, it is preferably 95.0 mol% or less, more preferably 90.0 mol% or less, and 80.0 mol% or less. Is more preferable.
  • the solid electrolyte (A) may be an amorphous sulfide solid electrolyte or a crystalline sulfide solid electrolyte, but if it is a crystalline sulfide solid electrolyte, the crystallite diameter of the sulfide solid electrolyte glass ceramics may be large. It is preferable because it becomes large.
  • Solid electrolyte (B) The solid electrolyte (B) obtained by the present embodiment is a product of the step (B), is a production intermediate of the sulfide solid electrolyte glass ceramics, and contains a lithium atom, a sulfur atom, and a phosphorus atom. It is preferable to use PS 43- as the main skeleton.
  • the solid electrolyte (B) may be an amorphous sulfide solid electrolyte or a crystalline sulfide solid electrolyte. If it is an amorphous sulfide solid electrolyte, it can be made into a sulfide solid electrolyte glass ceramics by heating (crystallization) described later. When it is a crystalline sulfide solid electrolyte, it can be used as a sulfide solid electrolyte glass ceramics, but it can also be further heated to proceed with crystallization.
  • the solid electrolyte (B) is preferably amorphous.
  • the solid electrolyte (B) contains a halogen atom, and typical ones containing a halogen atom include, for example, Li 2 SP 2 S 5 -LiI, Li 2 SP 2 S 5 -LiCl, Li 2 .
  • Solid electrolytes containing, for example, Li 2 S-P 2 S 5 -Li 2 O-LiI, Li 2 S-SiS 2 -P 2 S 5 -Li I, etc. are preferable.
  • a solid electrolyte composed of lithium sulfide, phosphorus sulfide and lithium halide, such as 5 -LiI-LiBr, is preferable.
  • the type of atom constituting the solid electrolyte (B) can be confirmed by, for example, an ICP emission spectrophotometer.
  • the P2 S 6 4- phosphorus ratio obtained from the solid 31 P - NMR measurement of the solid electrolyte (B), which is a production intermediate is 15.0 mol% or less. It is preferable to improve ionic conductivity and water resistance, more preferably 10.0 mol% or less, and further preferably 7.0 mol% or less from the viewpoint of improving ionic conductivity and water resistance.
  • the lower limit is not particularly limited because it is preferable not to contain P 2 S 6 4- in order to improve ionic conductivity and water resistance and to suppress the irreversible capacity of the battery.
  • the solid electrolyte (B) obtained in the present embodiment has at least Li 2 SP 2 S 5, the molar ratio of Li 2 S to P 2 S 5 obtains higher ionic conductivity. From the viewpoint, 65 to 85:15 to 35 is preferable, 70 to 80:20 to 30 is more preferable, and 72 to 78:22 to 28 is further preferable.
  • the solid electrolyte (B) obtained in the present embodiment is, for example, Li 2 SP 2 S 5 -Li I-Li Br
  • the total content of Li 2 S and P 2 S 5 is 60 to 95 mol. % Is preferred, 65-90 mol% is more preferred, and 70-85 mol% is even more preferred.
  • the ratio of lithium bromide to the total of lithium bromide and lithium iodide is preferably 1 to 99 mol%, more preferably 20 to 90 mol%, further preferably 40 to 80 mol%, and even more preferably 50 to 70 mol. % Is particularly preferable.
  • the compounding ratio (molar ratio) of the lithium atom, the sulfur atom, the phosphorus atom and the halogen atom is 1.0 to 1.8: 1.0 to 2.0: 0. .1 to 0.8: 0.01 to 0.6 is preferable, and 1.1 to 1.7: 1.2 to 1.8: 0.2 to 0.6: 0.05 to 0.5 is more preferable. It is preferable, and more preferably 1.2 to 1.6: 1.3 to 1.7: 0.25 to 0.5: 0.08 to 0.4.
  • the compounding ratio (molar ratio) of lithium atom, sulfur atom, phosphorus atom, bromine, and iodine is 1.0 to 1.8: 1.0 to 2. 0: 0.1 to 0.8: 0.01 to 0.3: 0.01 to 0.3 is preferable, and 1.1 to 1.7: 1.2 to 1.8: 0.2 to 0. 6: 0.02 to 0.25: 0.02 to 0.25 is more preferable, 1.2 to 1.6: 1.3 to 1.7: 0.25 to 0.5: 0.03 to 0.
  • the shape of the solid electrolyte (B) is not particularly limited, and examples thereof include particles.
  • the average particle size (D 50 ) of the particulate solid electrolyte (B) can be exemplified in the range of 0.01 ⁇ m to 500 ⁇ m and 0.1 to 200 ⁇ m, for example.
  • the exothermic peak of the sulfide solid electrolyte glass ceramics of the present embodiment is preferably 120 ° C. or higher and 300 ° C. or lower, more preferably 150 ° C. or higher and 250 ° C. or lower, and 170 ° C. or higher and 220 ° C. or lower. More preferred.
  • the sulfide solid electrolyte glass ceramics of the present embodiment has a half-price width of the exothermic peak that first appears at a temperature of 130 ° C. or higher in the differential thermal analysis (DTA) of the solid electrolyte (B), which is a production intermediate.
  • DTA differential thermal analysis
  • the amorphous solid electrolyte (A) and the amorphous solid electrolyte (B) it is preferable to further heat the amorphous solid electrolyte (A) and the amorphous solid electrolyte (B).
  • the amorphous solid electrolyte (A) or the amorphous solid electrolyte (B) may be obtained and then heated.
  • the solid electrolyte (A) obtained in the step (A) may be heated to obtain a crystalline solid electrolyte (A) and then used as a raw material in the step (B), or may be used as a raw material in the step (B).
  • the amorphous solid electrolyte (B) obtained later in the step (B) may be heated to obtain sulfide solid electrolyte glass ceramics.
  • the heating temperature may be determined according to the structure of the sulfide solid electrolyte glass ceramics. Specifically, the amorphous solid may be determined.
  • the electrolyte (B) is subjected to differential thermal analysis (DTA) using a differential thermal analyzer (DTA device) under a temperature rise condition of 10 ° C./min, and the exothermic peak observed at the lowest temperature side at 130 ° C. or higher is performed. Starting from the peak top temperature, the temperature may be preferably 5 ° C. or higher, more preferably 7 ° C. or higher, still more preferably 10 ° C.
  • the lower limit is not particularly limited, but is preferably low temperature.
  • the temperature may be within 30 ° C. on the side, more preferably within 25 ° C. on the low temperature side. By setting such a temperature range, sulfide solid electrolyte glass ceramics can be obtained more efficiently and reliably.
  • a differential thermal analysis (DTA) is performed using a differential thermal analyzer (DTA device) under a heating condition of 10 ° C./min. ), And heat treatment is performed near the peak top of the exothermic peak.
  • the preferred heat treatment temperature is in the range of ⁇ 50 ° C. to 100 ° C., preferably in the range of ⁇ 30 ° C. to 80 ° C., and more preferably in the range of ⁇ 15 ° C. to 65 ° C., starting from the temperature at the top of the exothermic peak.
  • the heating temperature for obtaining the crystalline sulfide solid electrolyte (A) or the sulfide solid electrolyte glass ceramics varies depending on the structure of the obtained crystalline sulfide solid electrolyte (A) or the sulfide solid electrolyte glass ceramics. Therefore, although it cannot be unconditionally specified, it is usually preferably 130 ° C. or higher, more preferably 135 ° C. or higher, further preferably 140 ° C. or higher, and the upper limit is not particularly limited, but is preferably 350 ° C. or lower, more preferably. It is 330 ° C. or lower, more preferably 320 ° C. or lower.
  • the heating time is not particularly limited as long as the desired crystalline solid electrolyte (A) or sulfide solid electrolyte glass ceramics can be obtained, but for example, 1 minute or more is preferable, and 10 minutes or more is more preferable. , 30 minutes or more is more preferable, and 1 hour or more is even more preferable.
  • the upper limit of the heating time is not particularly limited, but is preferably 24 hours or less, more preferably 10 hours or less, further preferably 5 hours or less, still more preferably 3 hours or less.
  • the heating is preferably performed in an inert gas atmosphere (for example, nitrogen atmosphere, argon atmosphere) or a reduced pressure atmosphere (particularly in vacuum). This is because deterioration of the product (for example, oxidation) can be prevented.
  • the heating method is not particularly limited, and examples thereof include a method using a hot plate, a vacuum heating device, an argon gas atmosphere furnace, and a firing furnace.
  • a horizontal dryer having a heating means and a feeding mechanism, a horizontal vibration flow dryer, or the like can also be used, and may be selected according to the processing amount to be heated.
  • the present embodiment further preferably includes pulverizing the solid electrolyte (A), the solid electrolyte (B), or the sulfide solid electrolyte glass ceramics, and preferably includes a plurality of pulverization steps.
  • pulverizing the solid electrolyte (A), the solid electrolyte (B) or the sulfide solid electrolyte glass ceramics By pulverizing the solid electrolyte (A), the solid electrolyte (B) or the sulfide solid electrolyte glass ceramics, a sulfide solid electrolyte glass ceramics having a small particle size can be obtained while suppressing a decrease in ionic conductivity.
  • the crusher used for crushing the present embodiment is not particularly limited as long as it can crush the particles, and for example, a medium-type crusher using a crushing medium can be used.
  • a dry medium crusher such as a dry bead mill, a dry ball mill, or a dry vibration mill, or a dry crusher such as a dry non-medium crusher such as a jet mill can be used.
  • Wet bead mills, wet ball mills, wet vibration mills, etc. are typical examples, and dry bead mills or dry bead mills that use beads as a crushing medium because the conditions of crushing operation can be freely adjusted and it is easy to handle smaller pulverized particles. Wet bead mills are preferred.
  • the size of the beads used in the crusher may be appropriately selected according to a desired particle size, treatment amount, etc.
  • the diameter of the beads may be about 0.05 mm ⁇ or more and 5.0 mm ⁇ or less, preferably about 0.05 mm ⁇ or more and 5.0 mm ⁇ or less. It is 0.1 mm ⁇ or more and 3.0 mm ⁇ or less, more preferably 0.3 mm ⁇ or more and 1.5 mm ⁇ or less.
  • a machine capable of crushing an object using ultrasonic waves for example, a machine called an ultrasonic crusher, an ultrasonic homogenizer, a probe ultrasonic crusher, or the like can be used.
  • various conditions such as the frequency of the ultrasonic wave may be appropriately selected according to the average particle size and the like of the desired complex, and the frequency may be, for example, about 1 kHz or more and 100 kHz or less, so that the complex can be more efficiently formed. From the viewpoint of pulverization, it is preferably 3 kHz or more and 50 kHz or less, more preferably 5 kHz or more and 40 kHz or less, and further preferably 10 kHz or more and 30 kHz or less.
  • the output of the ultrasonic crusher may be usually about 500 to 16,000 W, preferably 600 to 10,000 W, more preferably 750 to 5,000 W, and further preferably 900 to 1,500 W. be.
  • the average particle size (D 50 ) of the complex obtained by pulverization is appropriately determined as desired, but is usually 0.01 ⁇ m or more and 50 ⁇ m or less, preferably 0.03 ⁇ m or more and 5 ⁇ m or less, and more. It is preferably 0.05 ⁇ m or more and 3 ⁇ m or less. By setting such an average particle size, it is possible to meet the demand for a solid electrolyte having an average particle size of 1 ⁇ m or less.
  • the time for crushing is not particularly limited as long as the complex has a desired average particle size, and is usually 0.1 hours or more and 100 hours or less, from the viewpoint of efficiently setting the particle size to a desired size. It is preferably 0.3 hours or more and 72 hours or less, more preferably 0.5 hours or more and 48 hours or less, and further preferably 1 hour or more and 24 hours or less.
  • a positive electrode mixture or a negative electrode mixture in which a sulfide solid electrolyte is attached to the surface of the active material can be obtained by heating the sulfide solid electrolyte glass ceramics together with the active material. ..
  • the positive electrode active material in relation to the negative electrode active material, it is possible to promote a battery chemical reaction accompanied by the movement of lithium ions due to a lithium atom preferably adopted as an atom that develops ionic conductivity in the present embodiment. If there is, it can be used without particular limitation.
  • the positive electrode active material capable of inserting and removing lithium ions include an oxide-based positive electrode active material and a sulfide positive electrode active material.
  • Oxide-based positive electrode active materials include LMO (lithium manganate), LCO (lithium cobalt oxide), NMC (lithium nickel manganese cobalt oxide), NCA (lithium nickel cobalt oxide), LNCO (lithium nickel cobalt oxide), and olivine type.
  • LMO lithium manganate
  • LCO lithium cobalt oxide
  • NMC lithium nickel manganese cobalt oxide
  • NCA lithium nickel cobalt oxide
  • LNCO lithium nickel cobalt oxide
  • the sulfide positive electrode active material examples include simple sulfur (S 8 ), lithium sulfide (Li 2 S), polysulfide (Li 2 S x ), titanium sulfide (TiS 2 ), molybdenum sulfide (MoS 2 ), and iron sulfide (MoS 2).
  • FeS, FeS 2 ), copper sulfide (CuS), nickel sulfide (Ni 3S 2 ) and the like can be mentioned.
  • niobium selenate (NbSe 3 ) or the like can also be used.
  • the positive electrode active material can be used alone or in combination of two or more.
  • an atom preferably adopted as an atom exhibiting ionic conductivity in the present embodiment preferably a metal capable of forming an alloy with a lithium atom, an oxide thereof, an alloy between the metal and a lithium atom, and the like can be used.
  • a metal capable of forming an alloy with a lithium atom, an oxide thereof, an alloy between the metal and a lithium atom, and the like can be used.
  • it can be used without particular limitation as long as it can promote a battery chemical reaction involving the movement of lithium ions due to a lithium atom.
  • the negative electrode active material capable of inserting and removing lithium ions those known as negative electrode active materials in the battery field can be adopted without limitation.
  • Examples of such a negative electrode active material include metallic lithium such as graphite, metallic lithium, metallic indium, metallic aluminum, metallic silicon, and metallic tin, metals that can form an alloy with metallic lithium, and oxides of these metals (titanic acid). (Titium, etc.), and alloys of these metals and metallic lithium, etc. can be mentioned.
  • the electrode active material used in the present embodiment may have a coating layer coated on the surface thereof.
  • the material for forming the coating layer the ionic conduction of an atom exhibiting ionic conductivity in the crystalline sulfide solid electrolyte used in the present embodiment, preferably a nitride, an oxide of a lithium atom, or a composite thereof, etc.
  • the body is mentioned.
  • a conductor having a lysicon type crystal structure such as Li 4-2 x Zn x GeO 4 having a main structure of lithium nitride (Li 3 N) and Li 4 GeO 4 , a Li 3 PO 4 type skeleton.
  • a conductor having a thiolysicon type crystal structure such as Li 4-x Ge 1-x P x S 4 having a structure, a conductor having a perovskite type crystal structure such as La 2 / 3-x Li 3 x TiO 3 , LiTi 2 (PO 4 ) Examples thereof include a conductor having a NASICON type crystal structure such as 3 .
  • lithium titanate such as Li y Ti 3-y O 4 (0 ⁇ y ⁇ 3), Li 4 Ti 5 O 12 (LTO), LiNbO 3 , LiTaO 3 and other metals belonging to Group 5 of the periodic table.
  • Lithium metallic acid Li 2 O-B 2 O 3 -P 2 O 5 system, Li 2 O-B 2 O 3 -ZnO system, Li 2 O-Al 2 O 3 -SiO 2 -P 2 O 5 -TIO
  • oxide-based conductors such as two -series.
  • a solution containing various atoms constituting the material forming the coating layer is attached to the surface of the electrode active material, and the electrode active material after the attachment is preferably 200 ° C. or higher and 400 ° C. or lower. Obtained by firing in.
  • a solution containing various atoms for example, a solution containing alkoxides of various metals such as lithium ethoxyde, titanium isopropoxide, niobium isopropoxide, and tantalum isopropoxide may be used.
  • an alcohol solvent such as ethanol and butanol
  • an aliphatic hydrocarbon solvent such as hexane, heptane and octane
  • an aromatic hydrocarbon solvent such as benzene, toluene and xylene
  • the above-mentioned adhesion may be performed by dipping, spray coating or the like.
  • the firing temperature is preferably 200 ° C. or higher and 400 ° C. or lower, more preferably 250 ° C. or higher and 390 ° C. or lower, and the firing time is usually about 1 minute to 10 hours from the viewpoint of improving manufacturing efficiency and battery performance. It is preferably 10 minutes to 4 hours.
  • the coverage of the coating layer is preferably 90% or more, more preferably 95% or more, still more preferably 100%, that is, the entire surface is preferably covered based on the surface area of the electrode active material.
  • the thickness of the coating layer is preferably 1 nm or more, more preferably 2 nm or more, and the upper limit is preferably 30 nm or less, more preferably 25 nm or less.
  • the thickness of the coating layer can be measured by observing the cross section with a transmission electron microscope (TEM), and the coverage can be determined from the thickness of the coating layer, the atomic analysis value, and the BET surface area. Can be calculated.
  • TEM transmission electron microscope
  • a current collector in addition to the positive electrode layer, the electrolyte layer and the negative electrode layer, and a known current collector can be used.
  • a layer in which a layer that reacts with the above-mentioned sulfide solid electrolyte, such as Au, Pt, Al, Ti, or Cu, is coated with Au or the like can be used.
  • the battery characteristics of the battery using the sulfide solid electrolyte glass ceramics of the present embodiment can be evaluated by, for example, the irreversible capacity at the initial cycle calculated from the CV measurement. It is preferable that the irreversible capacity is small because the capacity of the battery approaches the theoretical capacity.
  • the irreversible capacity can be measured by the method described in Examples.
  • the irreversible capacity is usually 70 mAh / g or less, preferably 60 mAh / g or less, more preferably 50 mAh / g or less, still more preferably 45 mAh / g or less.
  • Tube voltage 30kV
  • Tube current 10mA
  • X-ray wavelength Cu-K ⁇ ray (1.5418 ⁇ )
  • Optical system Concentration method
  • Slit configuration Solar slit 4 ° (both incident side and light receiving side), divergence slit 1 mm, K ⁇ filter (Ni plate 0.5%), air scatter screen 3 mm are used)
  • w full width at half maximum obtained by measurement
  • a straight line baseline is set for the peak shape obtained by the XRD measurement (see FIG. 2), the intensity of each point and the difference between the baselines are taken, and the XRD curve (see FIG. 3).
  • w, x 0 and ⁇ were determined.
  • ICP emission spectroscopic analyzer determination of composition
  • the powder of the sulfide solid electrolyte was weighed and collected in a vial in an argon atmosphere.
  • a KOH alkaline aqueous solution was placed in a vial, and the sample was dissolved while paying attention to the collection of sulfur, and diluted appropriately to prepare a measurement solution.
  • the obtained measurement solution was measured with a Paschen-Lunge type ICP-OES apparatus (SPECTOR RACOS manufactured by SPECTRO) to determine the composition.
  • SPECTOR RACOS manufactured by SPECTRO
  • the calibration curve solution was prepared by using 1000 mg / L standard solution for ICP measurement for Li, P and S, 1000 mg / L standard solution for ion chromatograph for Br, and potassium iodide (special grade reagent) for I. Two measurement solutions were prepared for each sulfide solid electrolyte, and each measurement solution was measured four times to calculate the average value. The composition was determined from the average of the measured values of the two measuring solutions. From the obtained elemental ratio, the ratio (I Li2S / I P2S5 ) of the mole fraction of Li 2S (I Li 2S) to the mole fraction of P 2 S 5 (IP 2S 5 ) was calculated.
  • Pulse series Single pulse 90 ° Pulse width: 3.2 ⁇ s Waiting time after FID measurement until the next pulse is applied: 60s MAS (magic angle spinning) rotation speed: 11 kHz Accumulation number: 64 times
  • the P 2 S 7 4- phosphorus ratio was defined as the sum of the ratio of P 2 S 7 4- glass phosphorus and the ratio of P 2 S 7 4- crystalline phosphorus. Moreover, when the peak of PS 43- crystal could not be sufficiently optimized by one pseudo Voigt function, it was separated by using two pseudo Voigt functions.
  • the phosphorus ratio was determined by the method according to (1-5-1) except that Table 3 was used as the chemical shift of each phosphorus-containing structure.
  • DTA Differential thermal analysis
  • the exposure test device (FIG. 4) includes a flask 10 for humidifying nitrogen, a static mixer 20 for mixing humidified nitrogen and non-humidified nitrogen, and a dew point meter 30 for measuring the water content of the mixed nitrogen (M170 / manufactured by VAISALA). DMT152), a double reaction tube 40 in which a measurement sample is installed, a dew point meter 50 for measuring the water content of nitrogen discharged from the double reaction tube 40, and a concentration of hydrogen sulfide contained in the discharged nitrogen are measured.
  • a hydrogen sulfide measuring instrument 60 (Model3000RS manufactured by AMI) is used as a main component, and these are connected by a pipe (not shown).
  • the temperature of the flask 10 is set to 10 ° C. by the cooling tank 11.
  • a Teflon (registered trademark) tube having a diameter of 6 mm was used for the tube connecting each component.
  • the notation of the tube is omitted, and instead, the flow of nitrogen is indicated by an arrow.
  • the evaluation procedure was as follows. About 0.15 g of the powder sample 41 was weighed in a nitrogen glove box having a dew point of ⁇ 80 ° C., placed inside the reaction tube 40 so as to be sandwiched between quartz wool 42, and sealed.
  • Nitrogen was supplied into the apparatus 1 from a nitrogen source (not shown) at 0.02 MPa.
  • the supplied nitrogen passes through the bifurcated branch pipe BP, and a part of the supplied nitrogen is supplied to the flask 10 and humidified. Others are directly supplied to the static mixer 20 as nitrogen that is not humidified.
  • the amount of nitrogen supplied to the flask 10 is adjusted by the needle valve V.
  • the dew point is controlled by adjusting the flow rates of unhumidified nitrogen and humidified nitrogen with a flow meter FM equipped with a needle valve. Specifically, the flow rate of unhumidified nitrogen is 800 mL / min, and the flow rate of humidified nitrogen is 10 to 30 mL / min. The dew point of the humidified nitrogen mixture) was confirmed.
  • the three-way cock 43 was rotated to allow the mixed gas to flow inside the reaction tube 40 for 4 hours.
  • the amount of hydrogen sulfide contained in the mixed gas that passed through the sample 41 was measured by the hydrogen sulfide measuring instrument 60.
  • the amount of hydrogen sulfide generated during this period was converted into 1 g of a sample and obtained (unit: cc / g).
  • the gas after the measurement was passed through an alkaline trap 70 in order to remove hydrogen sulfide. After exposing the sample for a predetermined time, the supply of humidified nitrogen was stopped, and the reaction tube 40 was sealed with unhumidified nitrogen.
  • the electrolyte for the separator layer is added to the battery cell having a diameter of 10 mm, and after pressing 3 times at 2.55 MPa / cm 2 with a SUS die, 3.5 mg of the measurement powder (1) is added and 5 . Pressed 3 times at 10 MPa / cm 2 . Further, from the opposite side of the measuring powder (1), the mixture was pressed three times at 2.55 MPa / cm 2 , 5.10 MPa / cm 2, and 7.64 MPa / cm 2 .
  • the electrolyte for the CV measurement separator was synthesized under the following conditions.
  • a reaction vessel is connected to a bead mill capable of circulating operation (trade name: Star Mill LMZ015, manufactured by Ashizawa Finetech Co., Ltd., filled with 456 g of beads made of 0.5 mm diameter zirconia), pump flow rate: 650 mL / min, bead mill peripheral speed: 12 m / s, Grinding treatment was carried out at a mill jacket temperature of 45 ° C. for 45 hours.
  • the obtained slurry was dried at room temperature (25 ° C.) under vacuum and then heated at 80 ° C. to obtain a white powder of an amorphous solid electrolyte. Further, the obtained white powder was heated at 195 ° C.
  • Separator-InLi foil (having a layer structure, "/" means each layer.
  • / In 9.5 mm ⁇ ⁇ 0.1 mm / Li 9 mm ⁇ ⁇ 0.1 mm / In 9.5 mm ⁇ ⁇ 0.1 mm) was provided, and the Ti foil was used to prevent adhesion to the SUS mold. In this state, it was further pressed once at 1.27 MPa / cm 2 .
  • the cell was fixed by four screws sandwiching an insulator so as not to cause a short circuit between the measuring powder (1) and the InLi foil, and the screws were fixed at 8 Nm with torque to obtain a measuring cell.
  • the obtained measuring cell was connected to a measuring instrument (manufactured by VSS-3 Biological), and a CV curve was obtained under the following conditions. Measurement temperature: 25 ° C Sweep speed: 0.1 mV / s Potential measurement range: Open circuit voltage (about + 1.9V) ⁇ + 5.0V ⁇ + 1.8V The obtained CV curve was re-plotted with the flowing current (CurrentI (mA)) and the passage of time (FIG. 18). From this, the capacity per mass of the sulfide solid electrolyte glass ceramics used was calculated, and this was integrated to determine the saturated capacity as the irreversible capacity (mAh / g) (FIG. 19).
  • Average particle size (D 50 ) The volume-based average particle size was measured using a laser diffraction / scattering type particle size distribution measuring device (“Partica LA-950V2 model LA-950W2”, manufactured by HORIBA, Ltd.). A dehydrated mixture of toluene (manufactured by Wako Pure Chemical Industries, Ltd., special grade) and tert-butyl alcohol (manufactured by Wako Pure Chemical Industries, Ltd., special grade) at a weight ratio of 93.8: 6.2 was used as a dispersion medium. After injecting 50 ml of the dispersion double into the flow cell of the apparatus and circulating it, the measurement target was added and ultrasonic treatment was performed, and then the particle size distribution was measured.
  • Partica LA-950V2 model LA-950W2 manufactured by HORIBA, Ltd.
  • the amount of addition to be measured is 90 to 90% for the red light transmittance (R) and 70 to 90% for the blue light transmittance (B) corresponding to the particle concentration on the measurement screen specified by the device. Adjusted to. Further, as the calculation conditions, 2.16 was used as the value of the refractive index of the measurement target, and 1.49 was used as the value of the refractive index of the dispersion medium. In setting the distribution form, the particle size was calculated by fixing the number of repetitions to 15 times.
  • a powder (solid electrolyte (A1)) was obtained by processing (mechanical milling) for 40 hours at a rotation speed of 370 rpm with a planetary ball mill without heating and cooling. It was confirmed that the obtained powder was an amorphous solid electrolyte by X-ray diffraction (XRD) measurement (FIG. 5). In addition, solid 31 P - NMR measurement was performed to evaluate the P2 S 7 4- phosphorus ratio (Table 4).
  • Process (B) Weigh 1.035 g of the solid electrolyte (A1) obtained in the step (A), 0.096 g ( 0.00209 mol) of Li 2S, and 0.369 g (133.845 g / mol) of Li I as lithium halide.
  • An amorphous solid electrolyte (B1) was obtained in the same manner as in the above step (A) except that 0.00276 mol) was added.
  • the results of X-ray diffraction (XRD) measurement and differential thermal (DTA) analysis of the amorphous solid electrolyte (B1) are shown in FIGS. 6 and 7, respectively.
  • Li 2 S produced in (2-1-2) was 0.433 g (0.00942 mol)
  • P 2 S 5 produced in (2--2-2) was 0.698 g (0.00314 mol)
  • lithium halide As a result, 0.369 g (0.00276 mol) of LiI, 53 g of zirconia balls having a diameter of 2 mm, and ethylbenzene (5 mL) as a solvent were placed in a planetary ball mill (Fritsch: model number P-7) zirconia pot (45 mL). It was completely sealed and the inside of the pot had an argon atmosphere.
  • the slurry was treated with a planetary ball mill at 500 rpm for 40 hours (mechanical milling) without heating and cooling, and the obtained slurry was dried at room temperature under vacuum and then heated at 80 ° C. to form a powder (amorphous solid). Electrolyte (C1)) was obtained. It was confirmed that the obtained powder was an amorphous solid electrolyte by X-ray diffraction (XRD) measurement.
  • XRD X-ray diffraction
  • Crystallization step The whole amount of the obtained amorphous sulfide solid electrolyte (C1) was heated at 195 ° C. for 2 hours on a hot plate in a glove box having an argon atmosphere. Then, it was slowly cooled and pulverized in a mortar in a glove box under an argon atmosphere to obtain a powder (sulfide solid electrolyte glass ceramics (C1)).
  • a peak derived from a crystal structure similar to that of Thioricicon Region II was observed by X-ray diffraction (XRD) measurement (FIG. 15), and it was confirmed that the powder was sulfide solid electrolyte glass ceramics (C1). ..
  • the result of the differential thermal (DTA) analysis of the sulfide solid electrolyte glass ceramics (C1) is shown in FIG.
  • Comparative Example 2 In the above (Comparative Example 1), the sulfide solid electrolyte of Comparative Example 2 was similarly used except that 10 zirconia balls (about 32 g) having a diameter of 10 mm were used and mechanically milled at 370 rpm without using a solvent. Obtained glass ceramics.
  • Example 2 Heating (crystallization) process (1st time)
  • the solid electrolyte (A1) obtained in the step (A) was heated at 250 ° C. for 3 hours in a glove box having an argon atmosphere. Then, it was slowly cooled and pulverized in a mortar in a glove box under an argon atmosphere to obtain a powder (crystalline solid electrolyte (A2)).
  • XRD X-ray diffraction
  • X-ray diffraction (XRD) measurement was performed on the obtained powder.
  • DTA differential thermal
  • Examples 3 to 5 In the above (Example 2), the amount of Li 2 S and P 2 S 5 used in the step (A), the temperature of the heating (crystallization) step (first time) (in the table, the heating temperature), the step ( The sulfide solid electrolyte glass ceramics (3) to (5) of Examples 3 to 5 were similarly changed except that the amounts of the solid electrolyte ( A2 ) and Li 2S used in B) were changed as shown in Table 4 below. ) Was obtained.
  • Process (A) The amorphous solid electrolyte (A4) was used in the same manner as in Example 1 (Step A) except that Li 2 S was 0.416 g (0.00905 mol) and P 2 S 5 was 1.084 g (0.00488 mol). Obtained.
  • Process (B) 0.966 g of the amorphous solid electrolyte (A4) obtained in the step (A) was weighed, 0.165 g ( 0.00359 mol) of Li 2S was added thereto, and 0.369 g of Li I (Li I) as lithium halide was added.
  • An amorphous solid electrolyte (B4) was obtained in the same manner as in the step (B) of Example 1 except that 0.00276 mol) was added.
  • the whole amount of the amorphous solid electrolyte (B4) obtained in the step (B) was heated at 180 ° C. for 2 hours on a hot plate in a glove box having an argon atmosphere. Then, it was slowly cooled and crushed in a mortar in a glove box under an argon atmosphere to obtain a powder (sulfide solid electrolyte glass ceramics (reference example)). For the obtained powder, a peak derived from a crystal structure similar to that of Thiolicycon Region II was observed by X-ray diffraction (XRD) measurement, and it was confirmed that the powder was a crystalline solid electrolyte (glass ceramic).
  • XRD X-ray diffraction
  • Example 6 Process (B) 1.051 g of the powder obtained in the heating (crystallization) step (first time) of Example 2 was weighed, 0.098 g (0.00213 mol) of Li 2S was added thereto, and Li I was further reduced to 0 as lithium halide. An amorphous solid electrolyte (B6) was obtained in the same manner as in Example 2 except that 0.138 g (86.845 g / mol, 0.00159 mol) of 213 g (0.00159 mol) and LiBr was added. The result of the X-ray diffraction (XRD) measurement is shown in FIG.
  • XRD X-ray diffraction
  • Example 7 In Example 4, 0.987 g of the powder obtained in the heating (crystallization) step (first time) of Example 4 was weighed, 0.092 g ( 0.00200 mol) of Li 2S was added thereto, and the halogen was further added. A sulfide solid electrolyte glass ceramics (7) was obtained in the same manner except that 0.214 g (0.00160 mol) of LiI and 0.208 g (0.00240 mol) of LiBr were added as lithium iodide.
  • Crystallization step The amorphous sulfide solid electrolyte (C2) was heated at 203 ° C. for 2 hours on a hot plate in a glove box having an argon atmosphere. Then, it was slowly cooled and pulverized in a mortar in a glove box under an argon atmosphere to obtain a powder (sulfide solid electrolyte glass ceramics (C3)).
  • reaction vessel was connected to a bead mill equipped with a circulation pump (trade name: Star Mill LME4, manufactured by Ashizawa Finetech Co., Ltd., filled with 8.7 kg of 0.5 mm diameter zirconia beads), and the pump flow rate: 2 L / min.
  • Bead mill peripheral speed Grinding and mixing with a bead mill for 4 hours under the condition of 12 m / sec to obtain a slurry containing an electrolyte precursor and a polar solvent.
  • the slurry charged into the reaction vessel was circulated at a flow rate of 600 mL / min using the pump in the bead mill device, the operation of the bead mill was started at a peripheral speed of 10 m / s, the peripheral speed of the bead mill was set to 12 m / s, and the outside was set.
  • Hot water (HW) was passed by circulation and reacted so that the discharge temperature of the pump was maintained at 70 ° C.
  • the slurry after the reaction was placed in a 5 L Schlenk bottle, dried at room temperature, and then heated at 110 ° C. under reduced pressure to remove the complexing agent contained in the electrolyte precursor to obtain an amorphous solid electrolyte.
  • Example 7 A sulfide solid electrolyte glass ceramic (C7) was obtained with reference to the description of Example 1 of Patent Document 2. The amounts of Li 2 S, P 2 S 5 , Li I and Li Br used were combined with Example 7 for comparison with the sulfide solid electrolyte glass ceramics (7) obtained in Example 7.
  • Example 1 the crystallite diameter, P2 S 6 4 - phosphorus ratio, and differential heat of the sulfide solid electrolyte glass ceramics obtained in each Example and Comparative Example (The exothermic peak temperature and calorific value, I Li2S / IP2S5 , conductivity and H2S generation amount by DTA) analysis were also evaluated in the same manner as in Example 1 (Tables 5 and 6).
  • Comparative Examples 1 and 2 correspond to Example 1
  • Comparative Examples 3 to 6 correspond to Example 6
  • Comparative Example 7 corresponds to Example 7.
  • Table 7 shows the D50 and irreversible capacity of the sulfide solid electrolyte glass ceramics obtained in Examples 2 and 6 and Comparative Examples 1, 2, 4 and 7.
  • the reference example is an example of sulfide solid electrolyte glass ceramics having a high P 2 S 6 4 -phosphorus ratio, but it was confirmed that the ionic conductivity decreases as the P 2 S 6 4- phosphorus ratio increases. rice field.
  • Comparative Examples 3 to 6 share the same raw materials as Example 6.
  • the sulfide solid electrolyte glass ceramics (C3) of Comparative Example 3 has a small crystallite diameter, but has a high P2 S 6 4- phosphorus ratio, so that the ionic conductivity is low and the amount of H 2 S generated is also inferior. It became a thing.
  • Comparative Examples 5 and 6 correspond to the sulfide solid electrolyte glass ceramics produced with reference to the production method described in Patent Document 3, but there is room for improvement in ionic conductivity.
  • Comparative Example 7 is a sulfide solid electrolyte glass ceramics (C7) corresponding to the solid electrolyte described in Patent Document 2, but the sulfide solid electrolyte glass of Example 7 corresponding to this. Compared with the ceramics (7), the ionic conductivity was low.
  • Table 7 summarizes the relationship between the irreversible capacity of the sulfide solid electrolyte glass ceramics obtained in Examples 2 and 6 and Comparative Examples 1, 2 and 4 and the average particle size (D 50 ). It was confirmed that the results of Example 2 were improved as compared with Comparative Examples 1 and 2. In addition, it was confirmed that the results of Example 6 were improved as compared with Comparative Example 4. It was confirmed that the irreversible capacity was improved when the P2 S 6 4 - phosphorus ratio decreased, and the same tendency was confirmed in other Examples, Comparative Examples and Reference Examples. It is presumed that the irreversible capacity was improved by reducing the P2 S 6 4 - phosphorus ratio, which traps Li ions and accelerates the deterioration of the battery.
  • crystalline sulfide solid electrolyte having high ionic conductivity and excellent battery performance.
  • the crystalline sulfide solid electrolyte obtained by the production method of the present embodiment is suitably used for batteries, particularly for batteries used in information-related devices such as personal computers, video cameras, mobile phones, and communication devices.

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Abstract

La présente invention vise à fournir électrolyte solide à base de sulfure de type vitrocéramique ayant une conductivité ionique élevée et une résistance à l'eau améliorée, et à fournir un procédé de fabrication de l'électrolyte solide à base de sulfure de type vitrocéramique.　L'invention concerne : un électrolyte solide à base de sulfure de type vitrocéramique qui présente des pics à 20,2° et 23,6° dans une mesure de diffraction des rayons X (XRD) à l'aide de rayons CuKα, le diamètre de cristallite étant de 30 nm ou plus, et un rapport phosphore P2S6 4- obtenu par spectroscopie RMN 31P à l'état solide étant de 4,5 % en moles ou moins. L'invention concerne en outre un procédé de fabrication de la vitrocéramique à électrolyte solide à base de sulfure.
PCT/JP2021/037459 2020-10-09 2021-10-08 Électrolyte solide à base de sulfure de type vitrocéramique et procédé de fabrication associé WO2022075471A1 (fr)

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US18/030,286 US20230378525A1 (en) 2020-10-09 2021-10-08 Sulfide solid electrolyte glass ceramic and manufacturing method for same
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2024029480A1 (fr) * 2022-08-03 2024-02-08 出光興産株式会社 Électrolyte solide en vitrocéramique et batterie au lithium-ion
WO2024190440A1 (fr) * 2023-03-10 2024-09-19 出光興産株式会社 Mélange d'électrode positive, procédé de fabrication de mélange d'électrode positive et batterie au lithium-ion

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2013016423A (ja) 2011-07-06 2013-01-24 Toyota Motor Corp 硫化物固体電解質材料、リチウム固体電池、および、硫化物固体電解質材料の製造方法
WO2018225526A1 (fr) 2017-06-09 2018-12-13 出光興産株式会社 Procédé de fabrication d'électrolyte solide au sulfure
JP2019200856A (ja) * 2018-05-14 2019-11-21 三星電子株式会社Ｓａｍｓｕｎｇ Ｅｌｅｃｔｒｏｎｉｃｓ Ｃｏ．，Ｌｔｄ． 硫化物系固体電解質の製造方法および全固体型二次電池の製造方法

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103052995B (zh) * 2010-08-05 2016-07-13 丰田自动车株式会社 硫化物固体电解质玻璃、锂固体电池和硫化物固体电解质玻璃的制造方法
JP2014089971A (ja) * 2013-12-18 2014-05-15 Toyota Motor Corp 硫化物固体電解質材料、リチウム固体電池、および、硫化物固体電解質材料の製造方法
JP6719202B2 (ja) * 2015-12-24 2020-07-08 出光興産株式会社 硫化物固体電解質、硫化物ガラス、電極合材及びリチウムイオン電池
JP2019200851A (ja) 2018-05-14 2019-11-21 トヨタ自動車株式会社 固体電解質、全固体電池および固体電解質の製造方法
JP6719037B1 (ja) 2018-11-22 2020-07-08 出光興産株式会社 固体電解質の製造方法及び電解質前駆体

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2013016423A (ja) 2011-07-06 2013-01-24 Toyota Motor Corp 硫化物固体電解質材料、リチウム固体電池、および、硫化物固体電解質材料の製造方法
WO2018225526A1 (fr) 2017-06-09 2018-12-13 出光興産株式会社 Procédé de fabrication d'électrolyte solide au sulfure
JP2019200856A (ja) * 2018-05-14 2019-11-21 三星電子株式会社Ｓａｍｓｕｎｇ Ｅｌｅｃｔｒｏｎｉｃｓ Ｃｏ．，Ｌｔｄ． 硫化物系固体電解質の製造方法および全固体型二次電池の製造方法

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
KANNO ET AL., JOURNAL OF THE ELECTROCHEMICAL SOCIETY, vol. 148, no. 7, 2001, pages A742 - 746
SOLID STATE IONICS, vol. 177, 2006, pages 2721 - 2725

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2024029480A1 (fr) * 2022-08-03 2024-02-08 出光興産株式会社 Électrolyte solide en vitrocéramique et batterie au lithium-ion
WO2024190440A1 (fr) * 2023-03-10 2024-09-19 出光興産株式会社 Mélange d'électrode positive, procédé de fabrication de mélange d'électrode positive et batterie au lithium-ion

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